Hydrocarbon conversion process

ABSTRACT

Hydrocarbon conversion process catalyst comprising an active metallic component comprising at least one metal having hydrocarbon conversion activity and at least one oxygenated phosphorus component, and a support component comprising at least one porous refractory inorganic oxide matrix component and at least one crystalline molecular sieve zeolite component.

This is a division of application Ser. No. 320,866, filed Nov. 13, 1981,now U.S. Pat. No. 4,460,698.

BACKGROUND OF THE INVENTION

This invention relates to improved catalytic compositions having utilityin hydrocarbon conversion processes. In a specific aspect, the inventionrelates to improved catalytic compositions having utility in hydrogentreating of hydrocarbon feed materials.

Catalytic compositions containing a catalytically active metalliccomponent deposed on a non-zeolitic, refractory inorganic oxide supportare well known as are numerous uses therefor. Familiar examples includepetroleum and synthetic crude oil hydrotreating and hydrocrackingcatalysts comprising a Group VIB and/or VIII metal such as cobalt,nickel molybdenum and/or tungsten deposed on a non-zeolitic, refractoryinorganic oxide such as alumina, silica, magnesia, etc. and olefinpolymerization catalysts comprising a Group VIB metal deposed on silicaor silica-alumina supports.

It also is known that the activity or performance of catalysts of thetype described hereinabove for reactions such as hydrocracking,disproportionation and oligomerization can be improved or modified byinclusion in the catalyst of a crystalline molecular sieve zeolitecomponent. Thus U.S. Pat. No. 3,649,523 (Bertolacini et al.) discloses ahydrocarbon conversion process, and particularly hydrocracking anddisproportionation of petroleum hydrocarbon feed materials, carried outin the presence of improved catalysts comprising a metallic componenthaving hydrogenating activity deposed on a support component comprisinga large pore crystalline aluminosilicate and a porous support materialsuch as alumina, silica or aluminum phosphate. U.S. Pat. No. 3,894,930and U.S. Pat. No. 4,054,539 (both Hensley) disclose hydrocracking in thepresence of improved catalysts comprising a metallic hydrogenatingcomponent and a support component comprising ultrastable large porecrystalline aluminosilicate and silica-alumina. U.S. Pat. No. 3,876,522(Campbell et al.) discloses preparation of lube oils by a process thatincludes a hydrocracking step in which there are employed catalystscontaining a composite of a crystalline aluminosilicate zeolitecomponent and a porous refractory oxide component such as alumina orsilica, such composite containing deposited or exchanged catalyticmetals. U.S. Pat. No. 4,029,601 (Wiese) discloses oligomerization ofalkenes using a cobalt oxide-active carbon composite supported on arefractory oxide such as silica or alumina and/or crystallinealuminosilicate zeolites. Other processes in which catalysts comprisingcatalytically active metals and a support component comprising a porousoxide and a crystalline molecular sieve zeolite are useful includeisomerization of alkylaromatics and alkylation of aromatics andparaffins.

It also is known that the performance of various catalysts containingcatalytically active metals deposed on a non-zeolitic, refractoryinorganic oxide support component can be improved or modified byinclusion of phosphorus in the catalytically active metallic componentor through the use of phosphorus compounds in catalyst preparation. Forexample, U.S. Pat. No. 3,287,280 (Colgan et al.) discloses that the useof phosphoric acid solutions of nickel and/or molybdenum salts toimpregnate non-zeolitic supports such as alumina or silica leads toimproved dispersion of catalytically active metals on the supportsurface and improved results in hydrodesulfurization of petroleumhydrocarbon feeds. The patentee also discloses that phosphoric acidresidues remaining in the catalyst impart thermal stability thereto.U.S. Pat. No. 3,840,472 (Colgan) contains a similar disclosure withrespect to the use of phosphoric acid impregnating solutions of activemetal salts. U.S. Pat. No. 4,165,274 (Kwant) discloses a two-stepprocess for hydrotreating and hydrocracking tar sands oils whereinhydrotreating takes place in a first stage in the presence of analumina-supported, fluorine and phosphorus-containing nickel-molybdenumcatalyst, after which hydrocracking is conducted in the presence of acatalyst-containing nickel and tungsten supported on a low-sodium,Y-type molecular sieve support component. U.S. Pat. No. 3,985,676(Rekers et al.) discloses catalysts for polymerization of olefinsprepared by deposition of various organophosphorus compounds of chromiumonto high surface area non-zeolitic supports such as silica orsilica-alumina followed by thermal activation of the result.

Notwithstanding similarities in the basic catalyticcomposition--catalytically active metal component deposed onnon-zeolitic refractory inorganic oxide support component--into whichphosphorus or crystalline molecular sieve zeolite components have beenincorporated according to the above-described proposals, the reportedeffects of the zeolite and phosphorus components are, in many respects,sufficiently unrelated as to mitigate against attempting to combine theeffects of the components into a single catalyst. For example, theimproved hydrocracking activity of the above-describedzeolite-containing catalysts typically would not be desired in ahydrodesulfurization or hydrodenitrogenation catalyst because in typicalhydrotreating processes employing such catalysts, it is preferred tolimit cracking. Similarly, the improved hydrodesulfurization activity ofphosphorus-promoted catalysts such as those of Colgan et al. would be oflittle consequence within the context of a cracking, alkylation,isomerization or disproportionation process. On the other hand, we havepreviously found that a phosphorus component incorporated into thehydrogenating component of certain hydrotreating catalysts exerts apromotional effect with respect to denitrogenation of high nitrogenfeeds while crystalline molecular sieve zeolite components incorporatedinto catalysts containing similar active metals but free of phosphorusexerts a promotional effect with respect to denitrogenation andhydrocracking reactions.

It also is known from Rabo, Zeolite Chemistry And Catalysis, ACSMonograph 171, American Chemical Society, pages 294-297 (1976), thatmany crystalline molecular sieve zeolites possess only limited stabilitywith respect to strong acids such as the phosphoric acid used accordingto Colgan et al. Accordingly, it can be speculated that attempts tocombine the promotional effects of phosphoric acid and crystallinemolecular sieve zeolites have been limited by concern over destructionof the zeolite component.

U.S. Pat. No. 3,617,528 (Hilfman), which is directed to preparation ofsupported nickel-containing catalysts by coextrusion of a phosphoricacid solution of nickel or nickel and Group VIB metal compounds and analumina-containing carrier, suggests the use of carriers containingsilica and alumina that are amorphous or zeolitic in nature. Column 2lines 39-43. Crystalline aluminosilicate zeolites specifically disclosedby Hilfman are mordenite, faujasite and Types A and U molecular sieves.Column 3 lines 42-46. Hilfman does not address the effect of the acid onzeolite integrity or crystallinity, nor is there any disclosure orsuggestion as to whether any zeolite employed in the disclosedpreparations would remain intact in the final catalyst. In fact, none ofthe disclosed crystalline aluminosilicate zeolites, or any other forthat matter, is employed in the patentee's examples. Further, U.S. Pat.No. 3,706,693 (Mickelson et al. '693) and U.S. Pat. No. 3,725,243 (Hasset al.) teach that exposure of zeolites to strong acids such asphosphoric acid destroys zeolite crystallinity and integrity. In fact,both Mickelson et al. '693 and Hass et al. are directed specifically tocatalyst preparations in which impregnation of crystallinealuminosilicate-containing supports with phosphoric acid solutions ofsalts of hydrogenating metals results in destruction of zeolitecrystallinity. Further, three of the four crystalline aluminosilicatezeolites specifically disclosed by Hilfman (faujasite, mordenite andType A molecular sieve) are included among the crystallinealuminosilicate zeolites that are preferred for use in Mickelson etal.'s and Hass et al.'s zeolite-destructive preparations. The aforesaidRabo publication teaches that among Zeolite A, faujasite and mordenite,only the latter exhibits appreciable acid stability.

U.S. Pat. No. 3,905,914 (Jurewicz et al.) is directed to preparation ofoxidation catalysts by mixing a vanadium compound, zirconium salt andhydrogen halide, and then adding phosphoric acid or a compoundhydrolyzable to phosphoric acid. The result is refluxed to form a gelwhich then is dried, or "used to impregnate a suitable carrier, such asalumina, alundum, silica, silicon carbide, silica-alumina, zirconia,zirconium phosphate and/or a zeolite." Column 2 lines 47-51. Jurewicz etal. does not identify any zeolites nor do the patentee's examplesillustrate preparation of a supported catalyst. Also, no considerationis given to acid stability of zeolites and there is no indicationwhether any zeolite used in the disclosed catalyst preparation wouldremain intact.

Similar to the Mickelson et al. '693 and Hass et al. patents discussedhereinabove, U.S. Pat. Nos. 3,749,663, 3,749,664 and 3,755,150 (allMickelson) are directed to impregnation of support materials withphosphoric acid solutions of salts of catalytically active metals.Although none of these patents discloses impregnation of supportmaterials containing a zeolite component, each patent expressly cautionsagainst exposure of supports containing aluminum ions to phosphoric acidat relatively low pH stating that reaction of the acid and aluminumdegrades the support, fouls the impregnating solution and results information of undesirable chemical forms in the finished catalyst. (SeeMickelson '663 at Column 8 lines 60-69, Mickelson '664 at Column 8 lines6-15, Mickelson '150 at Column 9 lines 12-21.)

U.S. Pat. No. 3,836,561 (Young) also deals with acid treatment ofcrystalline aluminosilicate zeolites. According to Young,alumina-containing compositions, including those containing crystallinealuminosilicate zeolites, are reacted with aqueous acids includinghydrochloric, sulfuric, nitric, phosphoric and various organic acids, ata pH below about 5 in the presence of an ionizable salt that is solublein the aqueous phase, and then the result is washed, dried and calcined.The result of such treatment is removal of aluminum from thealumina-containing composition, replacement thereof with metalliccations if the ionizable salt is one containing cations that can beexchanged into the zeolite, increased porosity and decreased bulk volumeof the catalyst. The resulting compositions are said to have utility asabsorbents, ion exchange resins, catalysts and catalyst supports.Acid-stable zeolites and the effects of acid treatment on zeolitecrystallinity are discussed at Column 2 lines 61-68. Of course, Young'sacid treatment differs from the use of phosphoric acid according to thepatents discussed hereinabove in that Young's purpose is to removealuminum from the composition rather than to incorporate phosphorus intoit. It also differs from the patents discussed hereinabove in that thedisclosed compositions lack a catalytically-active metallic componentdeposed on the alumina-containing carrier.

Other patents and publications that may be of interest to the presentinvention in disclosing treatment of crystalline molecular sievezeolites or compositions containing the same with phosphoric acid andother phosphorus compounds to incorporate phosphorus into the zeoliteare U.S. Pat. No. 3,962,364 (Young) and U.S. Pat. Nos. 4,274,982,4,276,437 and 4,276,438 (all Chu). According to these patents, suitablephosphorus compounds include halides, oxyhalides, oxyacids andorganophosphorus compounds such as phosphines, phosphites andphosphates. Incorporation of phosphorus according to these patents isreported to improve para-selectivity in alkylation reactions. Chu '982further discloses treatment of the phosphorus-containing zeolites withmagnesium compounds. Chu '437 discloses impregnation of the phosphorustreated compositions with solutions of gallium, iridium or thalliumcompounds. Chu 438 contains a similar disclosure with respect toimpregnation of compounds of silver, gold and copper. Both patentsdisclose use of acid solutions of the metals as impregnating solutions,with hydrochloric, sulfuric and nitric as well as various organic acidsbeing disclosed. None of these patents discloses or suggests the use ofphosphoric acid impregnating solutions nor is there any suggestion of acatalyst containing an active metallic component which containsphosphorus. Rather, the respective patentees' phosphorus is incorporatedinto the zeolite.

British No. 1,555,928 (Kouwenhaven et al.) discloses crystallinesilicates of specified formula having utility in a wide range ofhydrocarbon conversions. Impregnation of the silicates with catalyticmetals is disclosed as is promotion or modification with halogens,magnesium, phosphorus, boron, arsenic or antimony, (Page 6 lines 33-54);with incorporation of phosphorus into the silicate to improve alkylationselectivity, as in the above-described Chu patents, being specificallydisclosed.

It also is known that phosphine or other organophosphorus complexes ofvarious metal salts can be employed in preparation of various supportedcatalyst compositions. For example, U.S. Pat. No. 3,703,561 (Kubicek etal.) discloses catalysts for olefin disproportionation comprising areaction product of (1) an organoaluminum halide, aluminum halide orcombination thereof with each other or with another organometallichalide and (2) a mixture of a salt of copper, silver or gold with acomplexing agent which may be an organophosphine. Reaction of components(1) and (2) is conducted in the presence of a solvent for the reactants,in the substantial absence of air and at temperatures low enough toavoid decomposition of the reactants. It also is disclosed to providethe catalysts in supported form by impregnating a support such as anon-zeolitic, refractory inorganic oxide or a zeolite with the reactionproduct, or by impregnation with one of the reactants followed byaddition of the other. Kubicek et al. also states that if such supportedcatalysts are to be activated by calcination the calcination should takeplace prior to impregnation with the active species, i.e., the reactionproduct of components (1) and (2). It is unclear whether residues of anyorganophosphine compound used in preparation of the catalysts of Kubiceket al. would remain in association with the active metallic species. Inany event, the catalyst preparation according to this patent isconducted under conditions designed to avoid conversion of any suchorganophosphine residues to an oxygenated phosphorus component such asthat required according to the present invention.

U.S. Pat. No. 3,721,718 (Hughes et al.) and U.S. Pat. No. 4,010,217(Zuech) contain disclosures similar to that of Kubicek et al. withrespect to use of organophosphorus complexes of various metal salts inpreparation of olefin disproportionation catalysts. Like Kubicek et al.,both Hughes et al. and Zuech contemplate supported catalysts; however,both patentees also state that if activation by calcination is desired,it should be accomplished by calcination of support prior toincorporation of active metals.

Another patent disclosing the use of metal complexes in catalystpreparation is U.S. Pat. No. 3,849,457 (Haag et al.) which is directedto preparation of carboxylic acids by hydrogenolysis of esters. Thecatalysts of Haag et al. comprise a hydrogenating metal component and asolid acid component such as a zeolite which components may be employedas a loose physical admixture or by combining the two components into asingle particle. Various methods for combining the two components into asingle particle are disclosed at Column 6 line 64-Column 7 line 44. Oneof these involves mixing a solution of a metal pi-complex with the acidsolid and then decomposing the complex to form elemental metal anddepositing the elemental metal onto the acid solid. A specific metalcomplex employed in this preparative scheme istetra(triphenylphosphine)palladium(II) dibromide. Another preparativemethod useful with respect to zeolitic acid solid components involvesincorporation of the hydrogenation component by conventional methodssuch as ion exchange or impregnation. None of the disclosed methodswould result in association of an oxygenated phosphorus component withthe metallic component of the patentees' catalyst.

U.S. Pat. No. 4,070,403 (Homeier) discloses a hydroformylation catalystcomprising a cobalt compound and a zeolite-alumina hydrosol dispersion.The cobalt compound is chemically bonded to the alumina-zeolitedispersion by a vapor-phase impregnation technique. Suitable cobaltcomponents of the disclosed catalysts include various salts such ashalides, nitrate and various carboxylates as well as organophosphinecomplexes. Homeier does not disclose or suggest the presence of anoxygenated phosphorus component in the final catalyst, nor does thepatentee attribute any promotional effect to phosphorus.

It can be appreciated from the foregoing that efforts to include both acrystalline molecular sieve zeolite component and a phosphorus componentin catalysts comprising an active metal component deposed on anon-zeolitic refractory inorganic oxide component in such a manner thatthe promotional effects of both the phosphorus and the zeolite areretained have been largely unsuccessful. In those instances in which anattempt has been made to incorporate a promoting phosphorus componentthrough the use of phosphoric acid impregnating solutions of compoundsof active metals, such use of phosphoric acid in conjunction with acrystalline aluminosilicate zeolite-containing composition often resultsin destruction of the crystalline aluminosilicate zeolite component.Other proposals such as those involving use of organophosphoruscomplexes of various metal salts to aid impregnation or deposition ofactive metals into or onto support result in only incidental, if any,incorporation of phosphorus into the final catalyst, and phosphorus soincorporated appears lacking in promotional effect.

It would be desirable to provide an improved catalytic composition inwhich both phosphorus and crystalline molecular sieve zeolite componentsare present in a form capable of exerting a promotional effect. It is anobject of this invention to provide an improved catalytic composition. Afurther object of the invention is to provide for the use of suchcatalytic compositions in hydrocarbon conversion processes. A stillfurther object is to provide for the preparation of catalysts in whichimproved performance is attained through incorporation of crystallinemolecular sieve zeolite and phosphorus components. Other objects of theinvention will be apparent to persons skilled in the art from thefollowing description and the appended claims.

We have now found that the objects of this invention can be attained byincorporation of an oxygenated phosphorus component into thecatalytically active metallic component of a catalytic composition andincorporation of selected crystalline molecular sieve zeolite componentsinto the support component of the composition. Advantageously, thecrystalline molecular sieve zeolite components of the invented catalystsare derived from acid-tolerant crystalline molecular sieve zeolites, andaccordingly, phosphorus component can be incorporated withoutsubstantial destruction of zeolite integrity or crystallinity. Further,the phosphorus component is incorporated into the metallic component ina form capable of exerting a promotional effect. Thus, as demonstratedin the examples appearing hereinbelow, the catalysts of the invention,wherein an oxygenated phosphorus component is incorporated into acatalytically active metallic component which is deposed on orassociated with a support component comprising at least one crystallinemolecular sieve zeolite component and a non-zeolitic, refractoryinorganic oxide matrix component, are superior to catalyst compositionsthat are identical but for the inclusion of a phosphorus component, orbut for inclusion of the zeolite component, in a variety of catalyticprocesses. Accordingly, the overall effect of the phosphorus and zeolitecomponents on performance of the basic catalytically active compositioncomprising a metallic component and a non-zeolitic, refractory inorganicoxide component is greater than the effect of either component alone ina variety of reactions.

In addition to the patents and publications discussed hereinabove, U.S.Pat. No. 4,228,036 (Swift et al.), and U.S. Pat. No. 4,277,373 (Sawyeret al.) may be of interest to the present invention in disclosingcatalytic compositions containing phosphorus and zeolite components.Specifically, Swift et al. discloses an improved catalytic crackingcatalyst comprising an alumina-aluminum phosphate-silica matrixcomposited with a zeolite component having cracking activity, such as arare earth-exchanged Y-type crystalline aluminosilicate zeolite. Swiftet al. does not disclose inclusion of an active metallic component intosuch catalysts. Further, in contrast to the catalysts of the presentinvention, wherein an oxygenated phosphorus component is included in anactive metallic component, the phosphorus component of Swift et al.'scatalysts is included in a refractory oxide material.

Sawyer et al. discloses hydroprocessing catalysts comprising a Group VIBand/or VIII metal component composited with an ultrastable Y-typecrystalline aluminosilicate zeolite and an alumina-aluminumfluorophosphate component. The catalyst also may contain an aluminagel-containing matrix. Although an essential component of Sawyer etal.'s catalyst is the aluminum fluorophosphate component of the support,it also is to be noted that patentee discloses use of phosphomolybdicacid to impregnate a support containing a Y-type crystallinealuminosilicate and alumina-aluminum fluorophosphate in Example 1 (seeColumn 5 lines 21-25). According to the example, however, it appearsthat there was no incorporation of a phosphorus component into theactive metal component of the catalyst because the table at Column 5lines 42-52 fails to report phosphorus content other than that containedin the aluminum fluorophosphate component of the support. Table 2 ofSawyer et al. also reports on a comparative catalyst C containingspecified levels of alumina, Y-type zeolite, nickel oxide, molybdenumoxide, and phosphorus pentoxide. For catalyst C to have been a faircomparator for the catalysts of Sawyer et al.'s invention, thephosphorus pentoxide component must have been present in a mannersimilar to the fluorophosphate component of the patentees' catalysts,i.e., as part of the support. As such, Sawyer et al. fails to discloseor suggest a catalyst containing phosphorus as an essential part of theactive metal component.

DESCRIPTION OF THE INVENTION

Briefly, the catalyst composition of this invention comprises (1) anactive metallic component comprising at least one metal havinghydrocarbon conversion activity and at least one oxygenated phosphoruscomponent; and (2) a support component comprising at least onenon-zeolitic, refractory inorganic oxide matrix component and at leastone crystalline molecular sieve zeolite component. According to afurther aspect of the invention, such catalytic compositions areprepared by a method comprising (1) impregnating a support componentcomprising at least one non-zeolitic, refractory inorganic oxide matrixcomponent and at least one acid-tolerant, crystalline molecular sievezeolite component with precursors to an active metallic componentcomprising at least one metal having hydrocarbon conversion activity andat least one oxygenated phosphorus component under conditions effectiveto retain substantial zeolite crystallinity; and (2) calcining theresult to convert active metallic component precursors to active form.According to a still further aspect of the invention, theabove-described catalytic compositions are employed in hydrocarbonconversion processes in which a hydrocarbon-containing chargestock iscontacted with the catalytic composition under hydrocarbon conversionconditions.

In greater detail, the invented catalytic composition comprises anactive metallic component and a support component. Relative proportionsof these are not critical so long as the active metallic component ispresent in at least a catalytically effective amount. Optimumproportions for a given catalyst will vary depending on intended use.Usefully, the active metallic component constitutes about 5 to about 50wt % and the support constitutes about 50 to about 95 wt %, such weightpercentages being based upon total weight of the catalytic composition.

The active metallic component of the invented catalyst comprises atleast one metal having hydrocarbon conversion activity and at least oneoxygenated phosphorus component. Suitable metals having hydrocarbonconversion activity include any of the metals typically employed tocatalyze hydrocarbon conversion reactions such as those of Groups IB,II, IIIB-VIIB and VIII. These can be present in the catalyst inelemental form, as oxides, as sulfides, or in other active forms.Combinations also are contemplated. The Group VIB metals exhibit a highdegree of susceptibility to promotion by oxygenated phosphoruscomponent. Accordingly, preferred compositions are those in which theactive metallic component comprises at least one Group VIB metal.

For a given catalyst, the preferred metal or combination of metals ofthe active metallic component will vary depending on end use. Forexample, in hydrogen processing of hydrocarbon feed materials such aspetroleum or synthetic crude oils, coal or biomass liquids, or fractionsthereof, preferred metals are those of Groups VIB and VIII such aschromium, molybdenum, tungsten, nickel, cobalt, iron, platinum, rhodium,palladium, iridium and combinations thereof. Oxides and sulfides ofthese are most preferred from the standpoint of catalytic performance.In processes for denitrogenation hydrotreating or denitrogenationhydrocracking, combinations of nickel and molybdenum and combinations ofnickel or cobalt with molybdenum and cLromium give particularly goodresults as discussed in in copending, commonly assigned U.S. Pat. No.4,431,527 of J. T. Miller et al. filed concurrently herewith.Particularly good results in hydrocracking processes are attained usingcatalysts containing combinations of cobalt and molybdenum, nickel andmolybdenum, or nickel and tungsten as the metals of the active metalliccomponent as discussed in detail in copending, commonly assigned U.S.Pat. No. 4,431,516 of M. J. Baird et al. filed concurrently herewith. Inmild hydrocracking processes such as catalytic dewaxing and catalyticcracker feed hydrocracking processes, preferred metals of the metalliccomponent are combinations of nickel and molybdenum as discussed indetail in copending, commonly assigned U.S. Pat. No. 4,431,517 of T. D.Nevitt et al. filed concurrently herewith.

In addition to the above-described catalytically active metal component,the active metallic component of the invented composition contains atleast one oxygenated phosphorus component which may be present in avariety of forms such as one or more simple oxides, phosphate anions,complex species in which phosphorus is linked through oxygen to one ormore metal or metals of the active metallic component or compounds ofsuch metal or metals, or combinations of these. The specific form of theoxygenated phosphorus component is not presently known; accordingly, forpurposes hereof, phosphorus contents are calculated and expressed interms of P₂ O₅.

Content of the metal and phosphorus components of the active metalliccomponent are not critical although phosphorus component preferably ispresent in at least an amount effective to promote hydrocarbonconversion activity of the metal or metals of the metallic component. Ingeneral, the metal or metals of the metallic component, calculated asoxide of the metal or metals in a common oxidation state, e.g., Cr₂ O₃,MoO₃, WO₃, NiO, CoO, make up about 3 to about 45 wt. % of the totalcatalyst weight while phosphorus component, expressed as P₂ O₅, makes upabout 0.1 to about 20 wt. % of the total catalyst. Within these broadranges, preferred levels of metal and phosphorus component will varydepending on end use. For example, catalysts useful in hydrogenprocessing of petroleum or synthetic crude oils, coal or biomassliquids, or fractions thereof preferably contain about 5 to about 35 wt.% Group VIB and/or VIII metal, expressed as common metal oxide, andabout 0.5 to about 15 wt. % oxygenated phosphorus component, expressedas P₂ O₅. Of course, higher and lower levels of metal and/or phosphoruscomponent can be present; however, below about 5 wt. % metal oxide,hydrogenation activity can suffer while above about 35 wt. %,improvements in activity typically do not compensate for the cost of theadditional metal. Similarly, below about 0.5 wt. % phosphorus component,calculated as P₂ O₅, promotional effect may be insignificant while aboveabout 15 wt. %, the phosphorus component may adversely affecthydrogenation activity or performance.

The support component of the invented catalytic composition comprises anon-zeolitic, refractory inorganic oxide matrix component and at leastone crystalline molecular sieve zeolite component. Suitablenon-zeolitic, refractory inorganic oxide matrix components are wellknown to persons skilled in the art and include alumina, silica,silica-alumina, alumina-silica, magnesia, zirconia, titania, etc., andcombinations thereof. The matrix component also can contain adjuvantssuch as phosphorus oxides, boron oxides, fluorine and/or chlorine.Matrix components that are preferred are those comprising alumina, owingto the availability and strength thereof. More preferably, the matrixcomponent is alumina, or a combination of alumina and silica.

The support component of the invented catalytic composition alsocomprises at least one crystalline molecular sieve zeolite component.This component of the support component is derived from at least oneacid-tolerant crystalline molecular sieve zeolite. For purposes hereof,an acid-tolerant crystalline molecular sieve zeolite is defined as onethat retains substantial crystallinity on exposure to phosphoric acid atpH down to about 3 to 4 and contains sufficiently low levels of cationscapable of reacting with aqueous phosphoric acid to form insoluble metalphosphates capable of plugging the zeolite's pores as to avoidsubstantial plugging. Both naturally occurring and synthetic zeolitesare contemplated. As with the metals of the metallic component of theinvented catalysts, the specific zeolite component to be included in agiven catalyst will vary depending on intended use of the catalyticcomposition. Examples of acid-tolerant, crystalline molecular sievezeolites include faujasite-type crystalline aluminosilicate zeolitesselected from the ultrastable Y-type crystalline aluminosilicatezeolites and Y-type crystalline aluminosilicate zeolites in acid andammonium forms, AMS-type crystalline borosilicate zeolites, ZSM-typecrystalline aluminosilicate zeolites and mordenite-type crystallinealuminosilicate zeolites.

The ultrastable crystalline aluminosilicate zeolites typically arefaujasite-type zeolites that exhibit improved stability at elevatedtemperatures, such stability being imparted by exchanging originalalkali metal cations with ammonium salt, calcining to convert thezeolite to hydrogen form, steaming or calcining again, exchanging withammonium salt once again and finally calcining. Specific examples ofultrastable Y-type crystalline aluminosilicate zeolites include zeoliteZ-14US, which is described in detail in U.S. Pat. No. 3,293,192 (Maheret al.) and U.S. Pat. No. 3,449,070 (McDaniel et al.), both of which areincorporated herein by reference. Y-type crystalline aluminosilicatezeolites in hydrogen or ammonium form also exhibit sufficientacid-tolerance as to be suitable for purposes of the present invention.When used in preparation of catalysts, Y-type zeolites in ammonium formare converted to acid form.

Crystalline borosilicate zeolites of the AMS-type are described indetail in commonly assigned U.S. Pat. No. 4,269,813 (Klotz), which isincorporated herein by reference. A specific example of this material iscrystalline borosilicate zeolite AMS-1B which corresponds to theformula:

    0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valance of n, Y ranges from 4to about 600 and Z ranges from 0 to about 160. AMS-1B provides an X-raypattern that comprises the following X-ray diffraction lines andassigned strengths:

    ______________________________________                                        d (Å)    Assigned Strength                                                ______________________________________                                        11.2 ± 0.2                                                                              W-VS                                                             10.0 ± 0.2                                                                              W-MS                                                             5.97 ± 0.07                                                                             W-M                                                              3.82 ± 0.05                                                                             VS                                                               3.70 ± 0.05                                                                             MS                                                               3.62 ± 0.05                                                                             M-MS                                                             2.97 ± 0.02                                                                             W-M                                                              1.99 ± 0.02                                                                             VW-M                                                             ______________________________________                                    

Crystalline aluminosilicate zeolites of the ZSM-type are well known andtypically contain silica and alumina in a molar ratio of at least 12:1(SiO₂ :Al₂ O₃) and have average pore diameters of at least about 5 Å.Specific examples of crystalline aluminosilicate zeolites of theZSM-type include crystalline aluminosilicate zeolite ZSM-5, which isdescribed in detail in U.S. Pat. No. 3,702,886; crystallinealuminosilicate ZSM-11, which ° . is described in detail in U.S. Pat.No. 3,709,979; crystalline aluminosilicate zeolite ZSM-12, which isdescribed in detail in U.S. Pat. No. 3,832,449; crystallinealuminosilicate zeolite ZSM-35, which is described in detail in U.S.Pat. No. 4,016,245; and crystalline aluminosilicate zeolite ZSM-38,which is described in detail in U.S. Pat. No. 4,046,859. All of theaforesaid patents are incorporated herein by reference.

Mordenite-type crystalline aluminosilicate zeolites also can be presentin the catalytic composition of the present invention. Suitablemordenite-type crystalline aluminosilicate zeolites are disclosed inU.S. Pat. No. 3,247,098 (Kimberline), U.S. Pat. No. 3,281,483 (Benesi etal.) and U.S. Pat. No. 3,299,153 (Adams et al.), each of which isincorporated herein by reference. Synthetic mordenite-structurecrystalline aluminosilicate zeolites, such as those designated Zeolonand available from the Norton Company of Worcester, Massachusetts, alsoare contemplated according to the invention.

Synthetic crystalline molecular sieve zeolites often are synthesized inalkali metal form, i.e., having alkali metal cations associated withframework species. For purposes of the present invention, the originalform as well as various exchanged forms such as the hydrogen (acid),ammonium and metal-exchanged forms are suitable. Crystalline molecularsieve zeolites can be converted to acid form by exchange with acids orby indirect means which typically involve contacting with ammonium oramine salts to form ammonium-exchanged intermediate species which can becalcined to acid form. Metal-exchanged zeolites are well known as aremethods for preparation thereof. Typically, zeolite is contacted with asolution or solutions containing metal cations capable of associatingwith framework metallic species. As noted hereinabove, crystallinemolecular sieve zeolite components present in the catalysts of thepresent invention contain only insubstantial levels of metals capable ofreacting with aqueous phosphoric acid to form insoluble metal phosphatescapable of plugging the pores of the support component. Accordingly,preferred metal-exchanged crystalline molecular sieve zeolites are thosein which the exchanged metals are nickel, cobalt, iron or a Group VIIInoble metal. In catalysts intended for use in hydrogen processing ofpetroleum or synthetic crude oils, coal or biomass liquids, or fractionsthereof, preferred crystalline molecular sieve zeolite components of theinvented catalysts are those in acid or polyvalent metal ion-exchangedform, and especially the former.

Content of non-zeolitic, porous refractory inorganic oxide matrixcomponent and crystalline molecular sieve zeolite component in thesupport component of the invented composition are not critical. Broadly,the matrix component constitutes about 5 to about 95 wt % of thesupport, and likewise, the zeolite component can constitute about 5 toabout 95 wt % of the support. Preferably, the content of thenon-zeolitic matrix component is at least about 10 wt % in order toensure that the support component will exhibit sufficient strength andphysical integrity to allow shaping of the component or final catalystinto a form suitable for intended use. Of course, even at less thanabout 10 wt % matrix component, suitable catalytic performance can beattained in applications amenable to use of catalyst in finely dividedform.

In terms of overall weight of the invented catalytic composition,preferred matrix content ranges from about 10 to about 90 wt % andpreferred zeolite content ranges from about 5 to about 90 wt %. Withinthese ranges, precise levels of matrix and zeolite components that aremore preferred for a given catalyst will vary depending on intended use.

The support component of the invented catalytic composition can beprepared by any suitable method. A preferred method comprises blendingacid-tolerant zeolitic component, preferably in finely divided form,into a sol, hydrosol or hydrogel of at least one inorganic oxide andadding a gelling medium such as ammonium hydroxide with stirring toproduce a gel. It also is contemplated to add the zeolite component to aslurry of the matrix component. In either case, the result can be dried,shaped if desired, and then clacined to form the support component.Suitable drying temperatures range from about 80° to about 350° F.(about 27° to about 177° C.) and suitable drying times range fromseconds to several hours. Calcination preferably is conducted at atemperature of about 800° to about 1,200° F. (about 427° to about 649°C.) for about 1/2 to about 16 hours. Shaping of the support componentcan be conducted if desired, preferably after drying or calcining.

Another suitable method for preparing the support component of theinvented composition comprises physically mixing particles of the matrixand zeolite components, each preferably in finely divided form, followedby thorough blending of the mixture.

The invented catalytic composition is prepared by a method comprising(1) impregnating the above-described support component with precursorsto the active metallic component under conditions effective to retainsubstantial zeolite crystallinity; and (2) calcining the result.

Impregnation of support component with precursors to the active metalliccomponent can be conducted in a single step or in a series of separatesteps which may be separated by drying and/or calcination steps,provided that impregnation with at least one metal precursor takes placeprior to or simultaneously with impregnation with phosphorus componentprecursor. If the active metallic component contains more than onemetal, precursors can be impregnated simultaneously, in sequence or byvarious combinations of simultaneous and sequential impregnations.Phosphorus component precursor or precursors can be included with one ormore of the metal precursors, or one or more separate phosphoruscomponent precursor impregnation steps can be included between or afterthe metal precursor impregnation steps. It also is contemplated toimpregnate either the porous refractory inorganic oxide matrix componentor the zeolitic component with precursors to the active metalliccomponent and blend the result with the other component.

The mechanics of impregnating a support with metallic componentprecursors are well known to persons skilled in the art and typicallyinvolve contacting a support with one or more solutions of one or moreprecursors in amounts and under conditions effective to yield a finalcomposition containing the desired amount of metal or metals. Suitablesolvents for the impregnating solution or solutions include water andvarious low boiling alcohols in which the precursors are soluble. Wateris preferred over alcohols from the standpoint of cost. In the case ofsimultaneous impregnations of metal and phosphorus component precursorsa more preferred solvent is aqueous phosphoric acid.

Metal precursors useful in preparation of the invented catalyticcompositions are well known to persons skilled in the art and include awide range of salts and compounds of the metals that are soluble in theimpregnating solvent and convertible to the desired form on calcination.Examples of useful salts include organic acid salts such as acetates,formates and propionates; nitrates; anhydrides; sulfates; and ammoniumsalts.

Useful precursors to the oxygenated phosphorus component are materialscapable of reaction with the metal or metals of the metallic component,or compounds of such metal or metals, or precursors thereto, so as toincorporate into the metallic component or metallic component precursora phosphorus-containing species that can be converted to an oxygenatedphosphorus component. From the standpoint of maximizing the promotionaleffect of the oxygenated phosphorus component, the preferred phosphoruscomponent precursor is one containing or capable of liberating phosphateanions as these are sufficiently reactive with the metal or metalprecursors to yield the desired promotional effect. Specific examples ofsuch phosphorus anion sources include phosphoric acid and salts thereofsuch as ammonium dihydrogen phosphate and diammonium hydrogen phosphate.Other phosphorus component precursors contemplated according to theinvention, though less preferred from the standpoint of attainingmaximum promotional effect, include organophosphorus compounds such aspartial and full esters of the aforesaid oxyacids such asorganophosphates and organophosphites; other organophosphorus compoundssuch as phosphines; and other phosphoric oxyacids such as phosphorus andphosphinic acids.

Impregnation of the support component with precursors to the metalliccomponent is conducted under conditions effective to avoid substantialdestruction of crystallinity of the crystalline molecular sieve zeolitecomponent. Preferably, such conditions include a temperature that ishigh enough to maintain the metal and/or phosphorus component precursorsin solution in the impregnating solvent though not so high as todecompose such precursors or have substantial adverse effects on thesupport component. More preferably, impregnating temperatures range fromabout 40° to about 200° F. pH of the impregnating solution or solutionsto be used also is important from the standpoint of insuring retentionof substantial zeolite crystallinity when phosphoric acid or otherphosphate anion source is employed as a phosphorus component precursorand/or impregnating solvent. In such cases, pH preferably issufficiently high that only insubstantial destruction of zeolitecrystallinity takes place during the preparation. Of course, the precisepH at which substantial decomposition of crystallinity will occur willvary somewhat depending upon the choice of zeolite component. Ingeneral, however, pH should be above about 2 in order to insureretention of sufficient zeolite crystallinity to insure desirablecatalytic performance. Most preferably, pH ranges from about 2.5 toabout 6 in order to insure retention of a high degree of zeolitecrystallinity while also insuring the desired association of thephosphorus and metal components of the active metallic component.

Following impregnation of the support component with metallic componentprecursors, it is preferred to dry the impregnated support. It also iscontemplated to dry the support subsequent to any intermediateimpregnating steps in a multi-step impregnation. Preferred dryingtemperatures range from about 80° to about 350° F. (about 27° to about177° C.), with preferred drying times ranging from a few seconds inspray drying operations to several hours in conventional driers.

Following impregnation of the support with precursors to the metalliccomponent and any optional drying steps, the impregnated support issubjected to calcination in order to convert at least a portion of themetal or metals of the metallic component to the active form and toconvert phosphorus precursors to oxygenated phosphorus component.Calcination is conducted in an atmosphere containing molecular oxygen ata temperature and for a period of time effective to attain the desiredconversion. Preferably, calcination temperatures range from about 800°to about 1,200° F. (about 427° to about 649° C.). Preferred calcinationtimes range from about 1/2 to about 16 hours.

As a result of the above-described preparation, there is attained acatalytic composition comprising (1) a metallic component comprising atleast one metal having hydrocarbon conversion activity and at least oneoxygenated phosphorus component, and (2) a support component comprisingat least one non-zeolitic, refractory inorganic oxide matrix componentand at least one crystalline molecular sieve zeolite component.Preferred compositions are those in which the zeolite component exhibitsat least about 40% crystallinity as compared to compositions identicalbut for inclusion of phosphorus component. More preferably, suchrelative crystallinity is at least about 75% in order to ensuredesirable catalyst performance.

The compositions of this invention have utility in a wide range ofhydrocarbon conversion processes in which a chargestock comprisinghydrocarbon is contacted with the catalyst under hydrocarbon conversionconditions. The invented catalysts are particularly useful in processesfor hydrogen processing of hydrocarbon feed materials such as wholepetroleum or synthetic crude oils, coal or biomass liquids, andfractions thereof. The process of the invention is described in furtherdetail with reference to hydrogen processing of such feed materials.

Petroleum and synthetic crude oil feeds that can be hydrogen processedaccording to this aspect of the invention include whole petroleum, shaleand tar sands oils, coal and biomass liquids and fractions thereof suchas distillates, gas oils and residual fractions.

Such feed materials are contacted with the catalyst of the inventionunder hydrogen processing conditions which will vary depending upon thespecific feed to be processed as well as the type of processing desired.Broadly, hydrogen treating temperatures range from about 350° to about850° F. (about 177° to about 455° C.), hydrogen pressures range fromabout 100 to about 3,000 psig (about 7 to about 210 kg/m²) and feedlinear hourly space velocities range from about 0.1 to about 10 volumesof feed per volume of catalyst per hour. Hydrogen addition rategenerally ranges from about 200 to about 25,000 standard cubic feet perbarrel (SCFB).

Examples of specific hydrogen treating processes employing the catalystsof this invention include hydrocracking of gas oil boiling rangehydrocarbons to gasoline boiling range products as disclosed in theaforesaid, copending, commonly assigned U.S. Pat. No. 4,431,516 of Bairdet al.; mild hydrocracking processes such as catalytic dewaxing andcatalytic cracker feed hydrocracking as disclosed in the aforesaidcommonly assigned U.S. Pat. No. 4,431,517 of Nevitt et al; anddenitrogenation and/or hydrocracking of high nitrogen feeds as disclosedin the aforesaid, commonly assigned U.S. Pat. No. 4,431,527 of Miller etal. and commonly assigned U.S. Pat. No. 4,406,779 of Hensley filedconcurrently herewith.

The present invention is described in further detail in the followingexamples, it being understood that the same are for purposes ofillustration and not limitation.

EXAMPLE 1

A support component containing 30 wt. % ultrastable Y-type crystallinealuminosilicate zeolite obtained from the Davison Chemical Division ofW. R. Grace and Co. dispersed in 70 wt. % alumina was prepared by mixing15,890 g alumina sol (10.0 wt. % alumina dry weight) with 681 gultrastable Y-type zeolite. To the result was added a solution of 400 mlwater and 400 ml concentrated NH₄ OH while stirring rapidly to form agel. The resulting gel was dried overnight at 250° F. in air, ground to100 mesh, mulled with water, extruded to 5/64" particles, driedovernight at 250° F. in air and calcined at 1000° F. in air for threehours.

A solution prepared by dissolving 8.30 g (NH₄)₂ Cr₂ O₇ in 49 ml waterwas added to 72.77 g of support component and allowed to stand for 1hour after which the result was dried in air at 250° F. for 1 hour.

Subsequently, 18.40 g (NH₄)₆ Mo₇ O₂₄.4H₂ O, 5.85 g Co(NO₃)₂.6H₂ O and8.6 g 85% phosphoric acid (H₃ PO₄) were dissolved in 35 ml water to forman impregnating solution having a pH of about 3. The impregnatingsolution was added to the chromia-impregnated support and the mixturewas allowed to stand for 1 hour after which the result was dried in airat 250° F. for 1 hour and calcined in air at 1000° F. for 1 hour.

The resulting catalyst contained 5.0 wt. % Cr₂ O₃, 15.0 wt. % MoO₃, 1.5wt. % CoO and 5.5 wt. % oxygenated phosphorus component, calculated asP₂ O₅.

EXAMPLE 2

A support component containing 50 wt. % ultrastable Y-type crystallinealuminosilicate zeolite (Davison) dispersed in 50 wt. % alumina wasprepared substantially according to the procedure of Example 1 using3863 g alumina sol (10 wt. % alumina) and 386.5 g ultrastable Y-typezeolite.

A solution prepared by dissolving 16.6 g (NH₄)₂ Cr₂ O₇ in 90 ml waterwas added to 148.98 g of the support component and allowed to stand for1 hour. The result was dried in air at 250° F. for 1 hour and calcinedin air at 1000° F. for 1 hour.

Subsequently, 36.8 g (NH₄)Mo₇ O₂₄.4H₂ O, 11.70 g Co(NO₃)₂.6H₂ O and13.02 g 85% H₃ PO₄ were dissolved in 67 ml water to form an impregnatingsolution having a pH of about 3. This solution was added to thechromia-impregnated support and the result was allowed to stand for 1hour after which the result was dried in air at 250° F. for 1 hour andcalcined in air at 1000° F. for 1 hour.

The resulting catalyst contained 5.0 wt. % Cr₂ O₃, 15.0 wt. % MoO₃, 1.5wt. % CoO and 4.0 wt. % oxygenated phosphorus component, calculated asP₂ O₅.

EXAMPLE 3

An impregnating solution having a pH of about 5.0 was prepared bydissolving 34.80 g cobalt nitrate, 42.45 g ammonium molybdate and 16.63g phosphoric acid in 600 ml distilled water, after which total volume ofthe solution was brought to 660 ml with distilled water. Theimpregnating solution was added to 331 g of a premixed support componentcontaining 41 wt. % ultrastable Y-type crystalline aluminosilicatezeolite and 59 wt. % silica-alumina and stirred vigorously for a shorttime. The result was dried in air at 250° F. for several hours, groundto pass a 28 mesh screen, formed into 1/8" pellets and calcined in airfor 1 hour at 500° F., for 1 hour at 750° F. and for 5 hours at 1000° F.

The resulting catalyst contained 9.13 wt. % MoO₃, 2.36 wt. % CoO and 2.3wt. % phosphorus component, calculated as P₂ O₅.

EXAMPLE 4

A support component containing 35 wt. % ultrastable Y-type crystallinealuminosilicate zeolite (Davison) dispersed in 65 wt. % silica-aluminacontaining 71.7 wt. % silica was prepared in two batches by blending4160 g of silica-alumina slurry containing about 2.5 wt. % solid with54.4 g of the zeolite component for about 5 to 10 minutes and thenfiltering, drying the solid in air at 250° F. overnight, grinding thedried solid to pass through a 30-mesh screen and calcining in air at1000° F. for 3 hours.

An impregnating solution was prepared by dissolving 35.4 g cobaltnitrate, 41.6 g ammonium molybdate and 4.6 g phosphoric acid in 472 mldistilled water. 290 g of the support component were contacted with theimpregnating solution after which the result was dried in air at 250° F.overnight, ground to 28 mesh, formed into 1/8" pills and calcined in airat 500° F. for 1 hour, at 700° F. for 1 hour and at 1000° F. for 5hours.

The resulting catalyst contained 2.6 wt. % CoO, 9.6 wt. % MoO₃ and 0.6wt. % oxygenated phosphorus component, calculated as P₂ O₅.

EXAMPLE 5

147.84 g support component containing 20 wt. % AMS-type crystallineborosilicate zeolite dispersed in 80 wt. % alumina was impregnated witha solution prepared by dissolving 22.09 g (NH₄)₂ Mo₇ O₂₄.4H₂ O and 13.63g Ni(NO₃)₂.6H₂ O in 68 ml distilled water and adding dropwise 7.44 g 85%H₃ PO₄ thereto while stirring. A small amount of water was added to theimpregnation mixture and the result was allowed to stand for 1 hour. Theresult was dried in air at 250° F. overnight, and then impregnated with22.09 g (NH₄)₂ Mo₇ O₂₄.4H₂ O, 13.63 g Ni(NO₃)₂.6H₂ O, and 7.44 g 85% H₃PO₄ in 68 ml distilled water. The result was allowed to stand for 2hours, dried in air at 250° F. and calcined at 1000° F.

The resulting catalyst contained 17.70 wt. % MoO₃, 3.44 wt. % NiO and4.35 wt. % oxygenated phosphorus component, calculated as P₂ O₅, and hada surface area of 242 m² /g and pore volume of 0.4802 cc/g.

EXAMPLE 6

The catalysts prepared in Examples 1 and 2 were tested fordenitrogenation and hydrocracking activity in an automated processingunit that included a vertical, tubular, downflow reactor having a lengthof 32" and inner diameter of 1/4". The unit included automatic controlsto regulate hydrogen pressure and flow, temperature and feed rate.Catalyst was ground to 14-20 mesh and loaded into a 10-12" segment ofthe reactor and sulfided therein by passing, 8 vol. % H₂ S in hydrogenover the catalyst at 300 psi for 1 hour at 300° F. followed by 1 hour at400° F. and then 1 hour at 700° F. The reactor then was heated tooperating temperature, pressured with hydrogen and a high nitrogen feedgenerated in situ from oil shale was pumped into the reactor using aRuska pump. The feed had the following properties:

    ______________________________________                                        API Gravity (°)                                                                            23.8                                                      Nitrogen (wt. %)    1.27                                                      Sulfur (wt. %)      0.65                                                      Oxygen (wt. %)      1.40                                                      Pour Point (°F.)                                                                           60                                                        Simulated Distillation (%)                                                    IBP- 360° F. 2.0                                                       360-650° F.  42.5                                                      650° F.+     55.5                                                      ______________________________________                                    

Operating conditions and results for each run are shown in Table 1. Inaddition to runs with the catalysts from Examples 1 and 2, comparativeruns were conducted using comparative catalysts A-C which were preparedaccording to the general procedure of Examples 1 and 2 but without theuse of phosphoric acid in the case of A and B and without a zeolitecomponent in the case of C. Compositions of catalysts A-C were asfollows:

(A) 10.0 wt. % Cr₂ O₃, 15.0 wt. % MoO₃ and 1.5 wt. % CoO supported on adispersion of 30 wt. % ultrastable Y-type crystalline aluminosilicatezeolite (Davison) in 70 wt. % alumina;

(B) 10.0 wt. % Cr₂ O₃, 15.0 wt. % MoO₃ and 1.5 wt. % CoO supported on adispersion of 50 wt. % ultrastable Y-type crystalline aluminosilicatezeolite dispersed in 50 wt. % alumina;

(C) 5.0 wt. % Cr₂ O₃, 15.0 wt. % MoO₃, 1.5 wt. % CoO and 4.6 wt. %oxygenated phosphorus component, calculated as P₂ O₅, supported onalumina.

                  TABLE 1                                                         ______________________________________                                        Catalyst     1       A       2     B     C                                    ______________________________________                                        Temp (°F.)                                                                          760     760     780   780   760                                  Pressure (psi)                                                                             1800    1800    1800  1800  1800                                 LHSV (hour.sup.-1)                                                                         0.5     0.5     0.5   0.5   0.5                                  Days on Oil  6       9       7     6     6                                    Liquid Product (g)                                                                         184     239     124   190   198                                  API Gravity (°)                                                                     40.0    36.5    49.4  49.6  37.0                                 Pour Point (°F.)                                                                    70      80      -40   -15   75                                   Sulfur (ppm) 2       110     6     262   57                                   Nitrogen (ppm)                                                                             1.7     173     0.7   3     85                                   Simulated                                                                     Distillation (%)                                                              IBP- 350° F.                                                                        14.5    10.7    44.5  42.0  9.0                                  350-650° F.                                                                         60.0    54.3    53.0  52.6  55.0                                 650° F.+                                                                            25.5    35.0    2.5   5.4   36.0                                 ______________________________________                                    

As can be seen from the table, catalysts 1 and 2 according to theinvention exhibited superior denitrogenation and desulfurizationactivity as compared to all three comparative catalysts. Further,cracking activities of catalysts 1 and 2 were superior to those ofcomparative catalysts A and B, respectively, as evidenced by thesimulated distillation data showing reduced 650° F. content. Crackingactivities of 1 and 2 also were superior to that of catalyst C whichlacked a zeolite component.

EXAMPLE 7

The catalysts prepared in Examples 3 and 4 were tested for hydrocrackingactivity in a vertical, tubular, downflow reactor having a length of191/2" and inner diameter of 0.55" and equipped with a pressure gaugeand DP cell to control hydrogen flow and a high pressure separator forremoval of products. The reactor was loaded with 18.75 g catalyst,immersed in a molten salt-containing heating jacket at 500° F. andpressured to 1250 psi with hydrogen. Temperature was held at 500° F. fortwo hours and then feed was pumped to the reactor with a Milton Roypump. Temperature was slowly increased to 680° F., held there overnightand then raised to operating temperature of 710°-730° F. Feed rate(LHSV) was 1-2 hr⁻¹. Runs were conducted for two weeks with periodicsampling.

The feed used in all runs was a mixture of 70 wt. % light catalyticcycle oil and 30 wt. % light virgin gas oil having the followingproperties:

    ______________________________________                                        API Gravity (°)                                                                            25.3                                                      Nitrogen (ppm)      304                                                       Sulfur (wt. %)      1.31                                                      Initial Boiling Point (°F.)                                                                404                                                       Final Boiling Point (°F.)                                                                  673                                                       ______________________________________                                    

In addition to the runs conducted using the catalysts of Examples 3 and4, comparative runs were conducted using comparative catalysts A-C whichare described below:

(A) 2.5 wt. % CoO and 10.2 wt. % MoO₃ supported on a dispersion of 35wt. % ultrastable Y-type crystalline aluminosilicate zeolite in 65 wt. %alumina prepared substantially according to the procedure of Example 3;

(B) commercial hydrocracking catalyst containing 2.63 wt. % CoO and 10.5wt. % MoO₃ supported on the base used in Example 3 obtained from theDavison Chemical Division of W. R. Grace and Co.;

(C) 2.6 wt. % CoO and 10.0 wt. % MoO₃ supported on a dispersion of 35wt. % ultrastable Y-type crystalline aluminosilicate zeolite (Davison)in 65 wt. % alumina and prepared substantially according to theprocedure of Example 4.

Hydrocracking activities of the catalysts were determined on the basisof temperature required to convert 77 wt. % of the feed to gasolineboiling range products (up to 380° F.). Activities relative tocomparative catalyst C are reported in Table 2.

                  TABLE 2                                                         ______________________________________                                        CATALYST  RELATIVE ACTIVITY INCREASE (%)                                      ______________________________________                                        A         102                2                                                B         126               26                                                3         144               44                                                C         100               --                                                4         138               38                                                ______________________________________                                    

As can be seen from the table, the phosphorus-promoted,zeolite-containing catalysts of the invention exhibited significantlyimproved hydrocracking activity as compared to the comparativecatalysts.

EXAMPLE 8

Activity of the catalyst of Example 5 for mild hydrocracking was testedin an automated pilot plant consisting of a downflow, vertical pipereactor of about 30" length and 3/8" inner diameter equipped with fourindependently wired and controlled heaters, a pressure step down andmetering device for introduction of hydrogen and an outlet pressurecontrol loop to control withdrawal of hydrogen. The catalyst of Example5 was calcined in air at 1000° F. for about 2 hours and then screened to14-20 mesh. The reactor was loaded to a height of twelve inches withglass balls after which about ten inches were loaded with 16 cm³ ofcatalyst. Glass balls were added to fill the reactor.

The reactor was heated 300° F. and a gaseous mixture of 8 vol % H₂ S inhydrogen was passed over the catalyst at 200 psi and 0.8 ft³ /hr. Afteran hour, temperature was raised to 400° F., and after another hour, to700° F. After one hour at 700° F., flow of the gaseous mixture wasdiscontinued and a hydrogen flow of 12000 SCFB at 1200 psi was begun.Heavy vacuum gas oil was pumped to the reactor at 10.2 cc/hr using apositive displacement pump. After passage through the reactor, productexited the reactor through a high pressure gas-liquid separator via avalve with a control loop designed to maintain a constant liquid levelin the high pressure separator. Feed properties were as follows:

    ______________________________________                                        API Gravity (°)  18.6                                                  Pour Point (°F.) 110                                                   Viscosity (cst at 100° C.)                                                                     11.68                                                 Carbon (wt. %)          84.94                                                 Hydrogen (wt. %)        11.63                                                 Nitrogen (wt. %)        0.166                                                 Sulfur (wt. %)          2.98                                                  Simulated Distillation (°F.)                                           IBP                     409                                                    5%                     671                                                   10%                     727                                                   20%                     788                                                   40%                     863                                                   60%                     918                                                   80%                     977                                                   90%                     1000+                                                 Paraffins (wt. %)       19.7                                                  Naphthenes (wt. %)      34.7                                                  Monoaromatics (wt. %)   12.6                                                  Polyaromatics and       33.0                                                  Heterocyclics (wt. %)                                                         ______________________________________                                    

In addition to the catalyst from Example 5, a comparative catalyst (A)containing 3.5 wt. % NiO, 10 wt. % Cr₂ O₃ and 15 wt. % MoO₃ supported ona dispersion of 20 wt. % rare earth-exchanged ultra-stable Y-typezeolite in 80 wt. % alumina was tested. Another run was conducted usinga catalyst (B) containing 20 wt. % MoO₃, 3.5 wt. % NiO and 3.0 wt. %oxygenated phosphorus component, calculated as P₂ O₅, supported onalumina.

Operating conditions and results are shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    RUN NO./SAMPLE NO. 1/1 1/2 1/3 1/4 1/5 1/6 2/1 2/2 2/3 3/1 3/2                __________________________________________________________________________    CATALYST           5   5   5   5   5   5   B   B   B   A   A                  TEMP (°F.)  700 740 740 690 730 730 740 780 780 740 780                PRESSURE (psi)     1200                                                                              1200                                                                              1200                                                                              1200                                                                              1200                                                                              800 1200                                                                              1200                                                                              1200                                                                              1200                                                                              1200               LHSV (hour.sup.-1) 0.625                                                                             0.625                                                                             0.625                                                                             0.625                                                                             0.625                                                                             0.625                                                                             0.68                                                                              0.68                                                                              0.68                                                                              0.625                                                                             0.625              HYDROGEN (SCFB)    12000                                                                             12000                                                                             12000                                                                             12000                                                                             12000                                                                             12000                                                                             12000                                                                             12000                                                                             12000                                                                             12000                                                                             12000              HOURS ON OIL       136 352 496 808 976 1312                                                                              128 320 488 110 158                API GRAVITY (°)                                                                           28.0                                                                              33.6                                                                              32.9                                                                              26.6                                                                              30.3                                                                              28.2                                                                              ND* 32.5                                                                              33.2                                                                              29.7                                                                              30.3               POUR POINT (°F.)                                                                          80  -70 -60 95  30  55  100 100 90  105 100                VISCOSITY (cst at 100° C.)                                                                4.71                                                                              2.51                                                                              2.55                                                                              6.07                                                                              3.88                                                                              3.89                                                                              ND  2.10                                                                              2.30                                                                              3.84                                                                              2.98               CARBON (wt. %)     87.00                                                                             86.90                                                                             87.05                                                                             87.09                                                                             87.02                                                                             87.26                                                                             86.78                                                                             86.97                                                                             87.06                                                                             87.01                                                                             87.16              HYDROGEN (wt. %)   12.93                                                                             13.09                                                                             12.94                                                                             12.80                                                                             12.96                                                                             12.66                                                                             13.19                                                                             13.02                                                                             12.93                                                                             12.97                                                                             12.82              SULFUR (ppm)       633 137 86  660 88  368 240 70  16  102 79                 NITROGEN (ppm)     135 8.8 14  409 29  338 22  3   1   76  137                SIMULATED DISTILLATION                                                        IBP                114 0   -15 409 ND* ND  1.87                                                                              97  147 9   151                 5%                329 165 168 584 ND  ND  343 244 267 364 322                20%                631 427 448 716 ND  ND  572 440 462 606 558                50%                797 696 707 830 ND  ND  769 656 678 786 753                80%                907 860 863 928 ND  ND  896 827 841 905 882                95%                990 967 961 999 ND  ND  985 931 941 990 969                % DESULFURIZATION  97.9                                                                              99.5                                                                              99.7                                                                              97.7                                                                              99.7                                                                              98.7                                                                              99.2                                                                              99.8                                                                              99.9                                                                              99.7                                                                              99.1               % DENITROGENATION  91.9                                                                              99.5                                                                              99.2                                                                              60.2                                                                              98.2                                                                              79.6                                                                              98.7                                                                              99.8                                                                              99.9                                                                              95.3                                                                              91.6               HYDROGEN CONSUMED (SCFB)                                                                         795 1045                                                                              940 700 930 635 990 940 870 825 890                YIELD (wt. %)                                                                 IBP-360°  F.                                                                              5.5 14.8                                                                              13.6                                                                              0   ND  ND  5.6 12.0                                                                              11.4                                                                              4.8 6.0                360-650° F. 17.9                                                                              25.7                                                                              24.7                                                                              10.4                                                                              ND  ND  22.9                                                                              37.2                                                                              34.3                                                                              20.1                                                                              23.3               650° F.+    75.4                                                                              53.9                                                                              55.3                                                                              88.9                                                                              ND  ND  70.1                                                                              48.0                                                                              51.6                                                                              74.0                                                                              64.9               __________________________________________________________________________     *ND stands for not determined.                                           

As can be seen from the table, all three catalysts exhibited highdesulfurization activity and catalysts 5 and B showed gooddenitrogenation. Cracking activity, as indicated by the yield data, wasgenerally comparable for catalysts 5 and B, both of which were superiorto catalyst A. Catalyst 5 was superior to both comparative catalysts interms of selective cracking of waxy components as evidenced by thereductions in pour point in runs using catalyst 5. Catalyst 5 also wassuperior in terms of overall performance in that comparable or betterresults were achieved with that catalyst at lower temperatures thanthose used in the comparative runs.

EXAMPLE 9

A series of catalyst compositions was prepared from various crystallinemolecular sieve zeolite and matrix components and aqueous phosphoricacid solutions of various metal salts (pH about 3) according to thegeneral procedure of Examples 1-5. A second series of catalysts wasprepared in similar fashion to contain identical levels of metals andsupport components but no phosphorus (PH about 5).

Samples of the catalysts were anlayzed by X-ray diffraction to determinethe effect of phosphoric acid on retention of zeolite crystallinity. Foreach pair of catalysts (with and without phosphoric and impregnation) ofidentical metals and support content, intensity of one or more X-raybands characteristic of the zeolite component and not subject tointerference by the metals of the catalysts were measured.

For each pair of catalysts, composition and crystallinity of thephosphorus component-containing catalyst relative to that of thephosphorus-free composition is reported in Table 4.

                  TABLE 4                                                         ______________________________________                                                                      RELATIVE                                                                      CRYSTAL-                                                                      LINITY                                          SAMPLE  COMPOSITION (wt. %)   (%)                                             ______________________________________                                        A       3.5% NiO, 18% MoO.sub.3, 3.4% P.sub.2 O.sub.5 /                                                     86                                                      50% USY.sup.(1), 50% Al.sub.2 O.sub.3                                 B       3.5% NiO, 18% MoO.sub.3, 3.4% P.sub.2 O.sub.5 /                                                     78                                                      50% Y.sup.(2), 50% Al.sub.2 O.sub.3                                   C       3.5% NiO, 18% MoO.sub.3, 3.4% P.sub.2 O.sub.5 /                                                     86                                                      50% ZSM-5.sup.(3), 50% Al.sub.2 O.sub.3                               D       1.5% CoO, 10% Cr.sub.2 O.sub.3, 15% MoO.sub.3,                                                      79                                                      4.6% P.sub.2 O.sub.5 /40% HAMS-1B.sup.(4),                                    60% Al.sub.2 O.sub.3                                                  E       1.5% CoO, 10% Cr.sub.2 O.sub.3, 15% MoO.sub.3,                                                      88                                                      4.6% P.sub.2 O.sub.5 /30% USY, 70% Al.sub.2 O.sub.3                   ______________________________________                                         .sup.(1) Ultrastable Ytype crystalline aluminosilicate zeolite.               .sup.(2) Ytype crystalline aluminosilicate zeolite.                           .sup.(3) Crystalline aluminosilicate zeolite ZSM5.                            .sup.(4) Crystalline borosilicate zeolite HAMS1B.                        

As can be seen, crystallinity of the compositions according to theinvention was quite high relative to compostions identical but forinclusion of phosphoric acid in preparation. 3.5% NiO, 18.0% MoO₃, 3.5%P₂ O₅ /30% USY, 70% Al₂ O₃ exhibited 66% crystallinity relative to adispersion of 30% USY in 70% Al₂ O₃.

We claim:
 1. A hydrocarbon conversion process comprising contacting achargestock comprising whole petroleum, shale oil, tar sand oil, coaland biomass liquids and fractions thereof, under hydrocarbon conversionconditions comprising a temperature of 350° F. to 850° F., a hydrogenpressure of 100 to 3,000 psig and a space velocity of 0.1 to 10 volumesof feed per volume of catalyst per hour, in the presence of a catalyticcomposition comprising (1) an active metallic component comprising atleast one metal having hydrocarbon conversion activity and at least oneoxygenated phosphorus component, and (2) a support component comprisingat least one non-zeolitic, porous refractory inorganic matrix componentand at least one crystalline molecular sieve zeolite componentcomprising a crystalline borosilicate zeolite or a crystallinealuminosilicate zeolite selected from the group consisting ofultrastable Y crystalline aluminosilicate zeolites and Y crustallinealuminosilicates in acid form or mixtures thereof.
 2. A hydrogenprocessing process comprising contacting a whole petroleum or syntheticcrude oil, coal or biomass liquid, or a fraction thereof with hydrogenunder hydrogen processing conditions comprising a temperature of 350° F.to 850° F., a hydrogen pressure of 100 to 3,000 psig and a spacevelocity of 0.1 to 10 volumes of feed per volume of catalyst per hour,in the presence of a catalytic composition comprising (1) an activemetallic oomponent comprising at least one metal having hydrogenationactivity and at least one oxygenated phosphorus component, and (2) asupport component comprising at least one non-zeolitic, porousrefractory inorganic oxide matrix component and at least one crystallinemolecular sieve zeolite component comprising a crystalline borosilicatezeolite or a crystalline aluminosilicate zeolite selected from the groupconsisting of ultrastable Y crystalline aluminosilicate zeolites and Ycrystalline aluminosilite zeolites in acid form or mixtures therof.